Method of producing monomeric olefins



July 4, 1950 E. v. MURPHREE METHOD QF PRODUCING MoNoMERIc oLEFINs 2 Sheets-Sheet 1 Filed Feb. 14, 1948 July 4, 1950 E. v. MURPHREE 2,514,332

METHOD oF PRoDUcING MoNoMERIc oLEFINs Filed Feb. 14, 1948 2 Sheets-Sheet 2 mAcTloNA-rol Moi FRESH poum/:El

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' rationofDelawarc pagina February '14, 194s, semi N. am

s clump. (c1. :so-ssa) The present invention relates to an. improved l process for depolymerizing olefin polymers and 1,-- ene dimers boil at 212-321 F., the isobutylene more speciilcally for obtaining the monomertrimers boil at 338356 from low boiling polymers of the tertiary olefin isobutylene with a minimum of undesired cracking and of undesired isomerization. The invention will be fully understood from the following description and accompanying drawings.-

In the drawings, Fig. 1 shows in diagrammatic form an apparatus adapted to the continuous depolymerization of isobutylene, lpolymers and indicates the flow of materials.

Fig. 2 shows diagrammatically another embodiment of the inventoi'n.

It is frequently'desired to depolymerize certain olefin polymers and to recover the oleilns in the form of their monomers. This may be a step in the purification o f the olen or it may be a step used when the polymerization isuninten-l tionaily brought about. In any event, it is desirable to conduct the depolymerization smoothly and as eil'ectively as possible with the least amount of cracking. The term depolymerization indicates a smooth clean reversal of the polymerization' reaction for splitting ol the monomeric units, while cracking refers to the irreversible reaction in which hydrocarbon species other than the monomer are formed in substantial amounts as well as gaseous by-products, e. g.,.hydrogen and methane, tar, and coke.

Heretofore, depolymerization has been carried out by heating the polymers in an externally heated tube to the depolymerization reaction temperature. In some instances the preheated polymers were contacted with catalysts. In such processes it has been difilcult to maintain a high yield of monomer vand it has been diillcult to avoid contamination of the monomer product by isomerized species. Tar and coke'are formed by cracking in the heating tube and also on the catalyst if the heat required for high conversion is supplied through the tube and if the catalyst becomes heated to a cracking temperature. Thus, in such processes, continuous high yields are not obtained, the product does not have the Y purity desired, and material losses are sustained.

It has been found, as a basis for the present invention, that the depolymerization process can be greatly improved by restricting the temperature to which the polymer reactants are heated and by supplying heat for the reaction in the form of sensible heat carried into the reaction zone by isomeric polymers or copolymers that are less reactive at the restricted reaction temperatures maintained in the reaction zone.

By the term butyleue copolymerslis meant codimer and cotrimer which may be formed by copolymerization of isobutylenev with normal butylenes or by isomerization ofthe butylene polymers, which tends to occur -to a limited ex` mediate the dimers and trimers kmers boil at S56-374 F.

. 2 K I tent during the depolymerization. The isobutyl- Some of the required endothermic heat of the depolymerization may be supplied in the form of sensible heat carried by a'fluidized catalyst but it is important not to risk overheating the cata.-

lyst so that it has a cracking temperature when it contacts the reactive polymers. By iiuidized is meant that the solid catalyst in a ilnely divided lor powdered form is suspended in a carrier gas or vapors to form a dense suspension which will flow through conduits much like a liquid, exhibiting both static and dynamic heads.

By means of the technique employed according to the present invention, it is possible to control the'reaction temperature to a remarkable degree and suppLv the requisite .heat of reaction for high cnversioli. The result is that th yield .0f

monomer is maintained at a -high level up to %'of theoretical with a minimum of cracking, i. e.. with better selectivity. The whole reaction. is smooth and subject to close regulation.

Referring to the drawing in more detail, Fig. 1,

numeral I denotes the feed tube through which the reactant polymer is fedto the reaction system. This polymer is ordinarily a liquid. volatile hydrocarbon polymer fraction, for example,

a fraction composed'of dimers and/or trimers of isobutylene which boil in the range 212-356 F.

The fresh polymer feed from tube I is brought into admixture with 1060%. by volume of hot recycle polymer which is introduced through a line 2. 'I'he stream of. the mixed polymers is forced by pump lthrough a heating tube I which is immersed in a uniform temperature heating medium, as for example, molten lead, contained within heating vessel 5.

After being heated to temperatures at which the mixed polymers are vaporized completely, as for example, to a temperature in the range of 500 F. to 800 F., the resulting vapors pass from the heating tube I into conuence with a iluidized stream of powdered depolymerizing catalyst which i'iows through line 6. The powdered catalyst lmay be at a temperature somewhat above that of the polymer vapors to quickly raise the temperature of the vapors to a maximum reaction temperature, but the maximum temperatures of the vapors and of the catalyst should not exceed 800 F. v

rThe suspension of the powdered catalyst carried by the polymer vapors enters the reaction vessel l which has the form of a vertical cylinder fitted with a conical bottom 8. `.A grid or screen 9 placed in the lower part of the vessel 1 above the inlet I0 of the vaporized feed carry- F., the codimers interv and the cotriaussen ing material. The suspended catalyst and vapors within the reaction vessel. 1 swirl turbulently around, giving the appearance of a boiling -liquid even tothe point that there is anupper level v|| for the dense suspension as shown in the drawdust separator lz, preferabiy of :ne cyclone or centrifugal type. is placed in the upper'porytion of vessel 1 so that the vapors leaving .the

.vessel by pipe I3 are substantially free of cata-'- lyst dust particles.- These vapors are rich in the monomer' but also contain some unreacted polymer of isobutylene and some` of the copolyin the fractionator |4 and at the bottom of thefractionator I4. These polymer condensates may be withdrawn as a side stream through pipe I8 and through line I9 to be returned through line 20 to line 2. Some of the fractionally condensed polymers fromfractionator I4 may be removed from-'the system through lines 2| and 22. A heating coil 34 provides reboiling. If any cata.-

iyst fparticles collect in the fractionator conderisates they may be removed by filtration.

The powdered catalyst within the reaction vessel 1 is, as stated, in'a iluidized condition and it may be withdrawn by the pipe 23 for transfer therethroughinto a reheater 2 4. This reheater may bev similar in most respects -to the depolymerizing reaction vessel 1, including a distribu tor screen 25 above a'conical bottom 26 and a dust separator 21 near the top of the cylindrical vessel 24. A carrier gas suchas steam is injected through tube 20 into the transfer line 23 to aid the flow of. the 'iluidized catalyst toward the reheater 24. Fuel gas, such as refinery gas or 4natural gas, is injected into the transfer line 23from line 29 for combustion in the reheater vessel 24, into which air is passed from line 30 tainedwithin heating vessel |03. Hot recycle polymer is admixed from pipe |04 with the fresh polymer passed vthrough the heating tube |02 in a proportion of about'lO to 60% by volume.

After the mixed polymers arevaporized and heated to the'desired reaction temperature in the range of 500 F. to 800 F., the resulting vapors pass from the heating tube |02 through line |05 into thedepolymerizing vessel |08.

The reaction vessel |06 has the form of a vertical cylinder fitted with a conical bottom I .01 and has a grid or screen |03- above the vapor feed inlet from pipe |05. Powdered catalyst is mainl tained in a dense" turbulent suspension above -the grid or screen |08 and up to a product is rich not only in isobutylene monomers,

Vbut contains some unreacted polymer of isobutylene and some copolymers or isomerized iso butylene polymers which did not undergo decomposition under the prevailing conditions set forth. This vapor product is passed by line ||I into the fractlonating tower II2, which is tted with a reiluxing cooling coil` ||3 at the top and an overhead vapor withdrawal line I|4,- through which the isobutylene monomer is taken on for recovery by condensation. Reboiling of the boti toms in tower |I2 is obtained by providing heating con m.

bottoms.

to support combustion. The fuel introduced into the reheater 24 is burned directly in the presence I of the powdered catalyst which is maintained in ailuidized condition .in the reheater24. In this manner, the powdered catalyst is reheated and freed of any carbonaceous deposits, then is ready for return through pipe `3| to line 6. Steam may vessel 24 after thesegases have been freed o dust in the dust separator 21.

If desired, hot products of combustion may be obtained in a separate chamber and the hot combustion gases fed to the reheating chamber 9, as.fo'r example, through pipe 30 for imparting heat to the catalyst in the reheater vessel 24. The temperature of the hot gases producedv in vessel 24 is controlled to prevent overheating the catalyst and to prevent deterioration of any catalyst which is sensitive to the eifects oi' elevated temperatures.

l With reference to Fig. 2, the fresh polymer is fed from pipe |00 by pump |0| through a heating tube |02. located in a uniform temperature heating medium, as for example, molten lead, con- The undecomposed polymers which can be utitoms may be withdrawn through pipes ||6 and ||1 for recycling by line IIB and pump I|9 to line may be removed by filtration. Pipe |22 is provided at the bottom of the reaction vessel |00 to remove catalyst when the unit is shut down.

In carrying out the process, the fresh polymer is fed either as a liquid or a vapor to the heating tube to be heated to a temperature that does not exceed 800 F. A heating medium that has a uniform temperature, such as a molten lead bath, insures that the isobutylene polymers being heated do not undergo undesired thermal-decomposition, which would give ri'se to the undesired cracking reaction impurities. Various types of heating media may be employed. such as diphenyl ether, high temperature steam, or combustion products for heating the polymer indirectly. Direct radiant heating of these tubes is avoided to avoid nonuniform heating,

In the apparatus shown diagrammatically in Fig. l, the bulk of the catalyst is maintained in the dense suspension mass within the reaction Avessel 1, and a minor portion of this catalyst is withdrawn continuously for reheating in the re- These polymer condensates and botsequently`.investi`gations on which this invention hot acid polymerization of mixed butylenes or in the recycled condensate, as described, serves to improve the operation in two ways.

polymerization and cracking under the conditions that have been set forth to be used in the depolymerization of the isobutylene polymers. Therefore. the butylene copolymers can be used to dilute the isobutylene polymers so that during 'the preheating step, there is less danger of overheating of the isobutylene polymers. Since the .temperature of the polymer feed is one of the limiting factors in determining the activity of the catalyst and the selectivity of the depolymerization, it is important to supply additional heat to the depolymerization zone in order to furnish the endothermic heat required for the conversion of the isobutylene polymers, and the copolymers heated to the reaction temperature are capable of supplying this heat when used in suitable proportions. The heat capacity of the isobutylene. polymers is of the order of 0.67 B. t. u. per pound in the reaction temperatures and it has been determined that this low heat capacity of the reactant is suflicient to give a conversion of only about 35%. Thus, the additional heat must be supplied to the reaction zone and preferably in an adiabatic manner (i. e., directly by the charged preheated feed materials instead of `by indirect heat exchange with surroundings) and that is why supplying most of the heat required in the form of sensible heat carried by the copolymers which 'Ihese copolymers-have been proved to be resistant to de-` is based were undertaken to determine the feasibility of preparing the high purity isobutylene.

An example of favorable operating conditions employed in accordance with the present invention is set forth as follows: g

Pressure. p. s. i. 100 Reaction zone temps. F. 600-650 Feed rates. v./v./hr.:

Fresh polymer 2.41 Copolymer .59 Wt. per cent conversion on fresh feed 96.6 Gas analysis:

Propane 0 Isobutylene 98.7 n-Butylene 0.3 n-Butane 1.0

When similar conditions are used without obtaining proper adiabatic conditions in a oncethrough process that does not dilute the fresh polymer with refractory copolymers, the temperature gradients from the reactor wall to various parts of the reaction range from 53 F. tov 190 F. and the heat input is far from sufficient for conversion above 65% or for giving a product purity above 95%.

Other comparative runs lowing table:

Polymrfeed containing 14% copolymer.

. Attapulaus clay catalyst are shown in the fol- Cat. inlet temp. F

509 526 v048. 701 780 802 Isobutylene product purity 94.4 97.1 97.9 97.7A 97.4 96.6

The above data indicates that excellent product purity was obtained at temperatures below 800 F. even though 14% copolymer was present and the ratio of recycle to fresh feed was about 1 dilute the reactive polymers is important. It is,

however, desirable to restrict the amount of copolymer because when the feed contains over 60% of the copolymer, there is a tendency for the product to become lowered in purity. The preferred proportion of the copolymer is in the range of 10% to 60% by volume based on the total feed.

It will be understood that the higher the reaction temperature within the prescribed range of 500 F. to 800 F., the shorter the time required for the depolymerization reaction; and that the greatr the amount of catalyst and the greater its activity, the less time is required. These factors may be balanced without any difficulty so as to give a yield upwards of 75% of the isobutylene monomer having the desired purity which is above 97%, As the temperature is raised to 800 F., the feed rate has to be increased to avoid excessive lowering in the purity of the product. At feed rates below 3.84 liquid volumes per volume of catalyst per hour the conversion is dependent only on the temperature. VIn general', the feed rates are of the order of 1.0 to 4 liquid volumes of the polymers per'volume of catalyst per hour.

In previous years isobutylene monomer of .9D-95% purity was quite satisfactory for the manufacture of various commercial high molecular weight polybutenes; however, with the development of isobutylene-diene. copolymers of the synthetic rubber type it was found important to have the visobutylene meet minimum specification requirements of at least 97% purity. Conto 9. With proper adiabaticconditions the temperature gradient in between the inlet and middle of the reaction was restricted to less than 10 F.

From numerous tests that have been made it has been proved that the butylene copolymers used to dilute the fresh isobutylene polymer feed in preheating do not have an adverse effect on the purity of the product. This is quite an unexpected discovery, considering the close similarity that the polymers and copolymers have in composition since both are isomeric Ca and Cn olens.

In the depolymerization operation pressures ranging upwardly from about atmospheric pressure may be used but it is preferred that the presl sure be of the order of 10 to 100 pounds per square inch gauge. In the process carried out with apparatus illustrated in Fig. 2, the heat for the reaction is supplied by the fresh feed polymers and by the recirculated polymers which is composed largely Iof butylene copolymersv while the catalyst remains within the depolymerization reaction vessel. The fluidized powdered catalyst, which remains in the reaction zone, acts as a temperature modifying medium and rapidly levels the texn- Although it has been indicated that some part 'aussen of the heat may be, supplied to the reaction zone by the 'circulated catalyst in a process carried out .as shown in Fig. 1 while the remaining part of the h'eat of reaction is supplied by the fresh feed polymer and the copolymer diluent, the most advantageous method of supplying most of the 'polymers to form from 10% to 60%.by volume of the total polymer feed which is preheated to a heat is through the copolymers in order to avoid the risk of overheating the catalyst and since only a moderate amount of heat has to be supplied through the heating tube to the polymers.

The powdered catalyst is employed in a fluidizedl form by being suspended in the polymer vapors or also in a carrier gas, preferably steam. In the depolymerizing reaction zone the polymer vapors and the monomer product vapors serve to maintain the catalyst in suspension. In the reheater vessel the gaseous fuel. the oxygen-containing gas, and the gaseous products of combustion serve the same purpose. i The powdered,

catalyst may be passed in a continuous cyclic path between the depolymerizer and the reheater without requiring a'ny mechanical means such as temperature between 500 F. and 800 F. and is contacted with the iluidized catalyst maintained with a powdered depolymerizing catalyst main- 'copolymers furnishes most of the endothermlc a pump, fan, or screw conveyor to obtain the flow of the uidized powdered catalyst. The density of the suspension may be decreased by the addition oi' gas or can be increased by withdrawing gas from the mixture. In using the two vessels as shown in Fig. l, the connecting iiow lines are in the form of U tubes. The gas and vapors are added to the legs of these U tubes which serve to keep the powdered material uidized as it is propelled through the tubes. The amount of gas or vapor present in the suspension on the down stream sides of the U tubes is generally considerably less than on the upstream` sides and the resulting diiference in density produced thereby in the two sides is suiiicient to create a pressure difference which overcomes the frictionof the flow. In this way, continuous circulation is obtained.

,The powdered catalyst, as indicated above, is preferably an activated clay or similar type of adsorbent silicate, for example, a synthetic magnesium silicate" such as Magnesol. The preferred type of catalysts are the activated clays, such as Florida earth, bentonitic types of clays which have been'acid'treated, for example, with sulfuric, hydrochloric or hydrofluoric acids. Synthetic gel catalysts, especially those of silicate or those of siilca admixed with magnesia or zirconia may also be employed.

It is claimed:

1. An improved process for selectively depolymerizing isobutylene polymers which are dimers and trimers to form substantially pure isobutylene monomer, which` comprises introducing a feed stream of said polymers mixed with butylene copolymers preheated to a temperature between 500 and 800 F. into contact with a heated iinely di vided depolymerization catalyst maintained at a temperature in the same range by sensible heat of the copolymers, uldizing said catalyst within said reaction zone so that the catalyst forms a den'se suspension having a predetermined upper level, withdrawing a gaseous product stream from above said upper level of the dense suspension,

freeing said gaseous product stream of catalyst particles, and fractionating from the gaseous product stream a gaseous stream composed substantially of pure isobutylene monomer.

2. The process as described in claim 1, in which the copolymers are fractionally condensed from said gaseous product stream and are' returned to be admixed with the feed of fresh isobutylene tained in a dense suspensionby the Bow of the vapors -within a depolymerization zone at 500 F.- 800 F., proportioning the amount ofthe copolymers to the polymer so that the sensible heat of heat required in the depolymerization of the polymer, and withdrawing a vapor stream rich in isobutylene monomer vwith vapors of the copolymers that remain undecomposed,

4. A process for selectively depolymerizing isobutylene polymers which are dimers and trimers in the presence of isomeric butylene copolymers to for-m substantially pure isobutylene. monomer, the steps which comprise preheating the isobutylene polymers in a feed stream containing 10 to 60 volume per cent of said isomeric butylene copolymers by indirect heat exchange with a uniform temperature heating medium to a temperature within the range of 500 F.800 F. prior to contact with a depolymerization catalyst, passing resulting vapors of the thus preheated feed stream prior to decomposition of isobutylene polymers contained therein up through a dense suspension of uidized solid catalyst maintained at a temperature in the range of 500 F.800 F. by sensible heat of feed materials contacted with the cata.- lyst, removing resulting isobutylene monomer and isomeric butylene copolymer vapors from said dense suspension of uidized catalyst to a fractionating zone, fractionally condensing the isomeric butylene copolymer vapors in said fractionation zone, withdrawing isobutylene monomer vapor from said fractionating zone, returning condemate of the isomeric butylene copolymers to said feed stream for admixture therein with isobutylene polymers, passing a portion of the iluidized catalyst from said dense suspension to a reheating zone wherein carbonaceous deposits on the catalyst undergo combustion in the pres-` said powdered catalyst is an activated adsorbent clay.

EGER V. MURPHREE.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 2,196,363 Robertson Apr. 9, A194.0 2,349,045 Layng et al.' May 16, 1944 2,361,978 Swearingen Nov. 7, 1944 

1. AN IMPROVED PROCESS FOR SELECTIVELY DEPOLYMERIZING ISOBUTYLENE POLYMERS WHICH ARE DIMERS AND TRIMMERS TO FORM SUBSTANTIALLY PURE ISOBUTYLENE MONOMER, WHICH COMPRISES INTRODUCING A FEED STREAM OF SAID POLYMERS MIXED WITH BUYLENE COPOLYMERS PREHEATED TO A TEMPERATURE BETWEEN 500 AND 800*F. INTO CONTACT WITH A HEATED FINELY DIVIDED DEPOLYMERIZATION CATALYST MAINTAINED AT A TEMPERATURE IN THE SAME RANGE BY SENSIBLE HEAT OF THE COPOLYMERS, FLUIDIZING SAID CATALYST WITHIN SAID REACTION ZONE SO THAT THE CATALYST FORMS A DENSE SUSPENSION HAVING A PREDETERMINED UPPER LEVEL, WITHDRAWING A GASEOUS PRODUCT STREAM FROM ABOVE SAID UPPER LEVEL OF THE DENSE SUSPENSION, FREEING SAID GASEOUS PRODUCT STREAM OF CATALYST PARTICLES, AND FRACTIONATING FROM THE GASEOUS PRODUCT STREAM A GASEOUS STREAM COMPOSED SUBSTANTIALLY OF PURE ISOBUTYLENE MONOMER. 